JPH0619090A - Silver halide color photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To improve the color developing property and color picture fastness by incorporating specified cyan coupler and a coupler. CONSTITUTION:This material contains a cyan coupler shown by formula I and a coupler expressed by formula II. In formula I, Za is -NH- or -CH(R3)-, Zb and Zc are -C(R4)= or -N=, R1, R2 and R3 are an electron-attracting group having a-Hammett substitution constant sigmap of >=0.20, and R4 is hydrogen atom or a substituent. In formula II, R1 -CONR4R5, -SO2NR4R5, etc., R2 is a group replaceable by a naphthalene ring, (k) is an integer of 0 to 3, R3 is a substituent, and X is hydrogen atom or a group capable of being released by the coupling reaction with an aromatic primary amine developer oxidant. In formula III, R<1> is alkyl, aryl or heterocyclic group, R<2> is aryl, and Z is hydrogen atom or a group released by coupling.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material which gives high color-forming property and color image fastness and retains these excellent performances and reduces the amount of color development waste liquid. The present invention relates to a method for processing a silver halide color photographic light-sensitive material which can be processed and has good processing stability.

[0002]

BACKGROUND OF THE INVENTION As cyan dye-forming couplers, phenol type and naphthol type couplers are predominant. On the other hand, in recent years, many cyan couplers having a novel mother structure have been proposed. As a coupler similar to the present invention, for example, the coupler disclosed in JP-A-63-141057 is a magenta coupler. Although the magenta coupler is certainly improved in color image fastness and color reproducibility, it has a great problem of hue improvement when used as a cyan coupler. In addition, a pyrrolopyrazole type coupler is presented in European Patent No. 456,226A for the purpose of improving the hue of a cyan dye image and improving the color reproducibility. These couplers described are considerably improved in color developability (high activity of coupling reaction with oxidized aromatic primary amine developer and high molecular extinction coefficient of dye formed), color image fastness, and hue of color developable dye. However, further improvements have been desired, and further improvements in low replenishment, rapid processability, and process stability have been demanded.

Regarding the above-mentioned phenol-type and naphthol-type couplers, the phenol-type couplers are as follows:
For example, 2-acylamino-5-alkylphenol type,
2,5-diacylaminophenol type, 2-ureido-
Typical examples of 5-acylamino type naphthol couplers include 2-carbamoyl-1-naphthol type couplers and amide group-containing couplers at the 5-position, and these couplers are specifically described in US Pat. No. 2,369. , 929, 2,801,171, 2,895,826,
No. 3,772,002, No. 4,052,212
No. 4, No. 4,146, 396, No. 4,228, 23
No. 3, No. 4,296,200, No. 2,772,1
No. 62, No. 3,758,308, No. 4,334.
011; West German Laid-Open Patent Publication No. 3,329,729;
European Patent Publication No. 121,365, US Patent No. 4,
327,173, 3,446,622, 4,333,999, 4,427,767, 4,451,559, 4,775,616,
European Published Patent Publication Nos. 271,323-271,325
U.S. Pat. Nos. 4,690,889 and 4,25
4,212, 4,296,199, JP-A-61
The couplers described in No. 42658 and the like can be mentioned. However, the basic performances required of these phenol-type and naphthol-type couplers as cyan couplers, for example, the activity of the coupling reaction with the aromatic primary amine color developer oxidant, the molecular extinction coefficient of the formed dye, and the spectral Absorption maximum wavelength, short wavelength green light, absorption density in blue light region, hue change due to color density, etc .; heat and humidity of color dye image, fastness to light, leuco of color dye in reducing atmosphere , A stability of a coloring dye such as a change in hue over time; and the like, but not all couplers, which have some drawbacks and are being further improved. Especially for stable processing, especially from the viewpoint of environmental protection, from the reduction of the waste amount of the color developing solution, the coupler showing the above-mentioned various performances such as stable photographic property at the high bromine ion concentration in the color developing solution in the low replenishment amount processing. Development was strongly desired.

[0004]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color developability and color image fastness. Second of purpose
Another object of the present invention is to provide a silver halide color photographic light-sensitive material having the first object and exhibiting stable processability, particularly stable photographic properties in a color developing solution having a high bromine ion concentration. A third object is to provide a processing method for processing with a color developing solution having a high bromine ion concentration.

[0005]

The above-mentioned object can be achieved by the silver halide color photographic light-sensitive material and the processing method thereof described below. (1) A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing a cyan coupler represented by the following general formula (Ia) A silver halide color photographic light-sensitive material comprising a coupler represented by the general formula (II) represented by the following chemical formula 5 or the general formula (III) represented by the following chemical formula 6. General formula (Ia)

[0006]

[Chemical 4]

In the general formula (Ia), Za represents --NH-- or --CH (R ₃ )-, and Zb and Zc represent --C (R ₄ ) = or --N =, respectively. R ₁ , R ₂ and R
₃ has a Hammett's substituent constant σ p value of 0.20, respectively.
The above-mentioned electron-withdrawing groups are represented. However, σ of R ₁ and R ₂
The sum of p values is 0.65 or more. R ₄ represents a hydrogen atom or a substituent. However, when two R _4's are present in the formula, they may be the same or different. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. In addition, R ₁ , R ₂ , R ₃ , R ₄ or X
The group may become a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. General formula (II)

[0008]

[Chemical 5]

In the formula, R ₁ is --CONR ₄ R ₅ , --SO _{2
NR 4 R 5, -NHCOR 4,} -NHCOOR 6, -N
HSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHSO
₂ NR ₄ R ₅ , R ₂ is a group capable of substituting on a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, and X is a hydrogen atom or an aromatic primary amine developer oxidant. Represents a group capable of leaving by a coupling reaction with. However, R ₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R _{2 s} may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring. In addition, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X which is bonded to each other via a divalent or divalent or higher valent group may be formed. General formula (III)

[0010]

[Chemical 6]

In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.

First, the compound represented by formula (Ia) will be described in detail. In the general formula (Ia), Za represents —NH— or —CH (R ₃ ) —,
b and Zc each -C (R ₄₎ = or represent -N =. Therefore, the cyan coupler represented by the general formula (Ia) of the present invention is specifically represented by the following general formulas (IIa) to (IX).
It is represented by a).

[0013]

[Chemical 7]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and X
Are synonymous with each in the general formula (Ia). ) In the present invention, the general formula (IIa), (IIIa) or (IVa)
The cyan coupler represented by the formula (3) is preferable, and the cyan coupler represented by the general formula (IIIa) is particularly preferable.

The cyan coupler of the present invention is an electron-withdrawing group in which R ₁ , R ₂ and R ₃ are all 0.20 or more,
Moreover, the sum of the σ _p values of R ₁ and R ₂ is 0.65 or more. R
The sum of the σ _p values of ₁ and R ₂ is preferably 0.70 or more, and the upper limit is about 1.8.

Each of R ₁ , R ₂ and R ₃ is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. An electron withdrawing group having a σ _p value of 0.35 or more is preferable, and an electron withdrawing group having a σ _p value of 0.60 or more is more preferable. The upper limit is an electron-withdrawing group of 1.0 or less. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
The rule of thumb was proposed by LP Hammett in
This is widely accepted today. There are σ _p and σ _m values for the substituent constants determined by Hammett's rule, and these values are described in many general textbooks.
For example, "De Lange's Hand book of Chemis" edited by JA Dean
try ”12th edition, 1979 (McGraw-Hill) and“ Special Issue on Chemistry ”, 122, 96-103 pages, 1979.
Detailed in the year (Nankodo). In the present invention, R ₁ , R ₂ and R ₃ are defined by the Hammett's substituent constant σ _p value, but it is not meant to be limited to only certain substituents known in the literature. Of course, even if the value is unknown in the literature, it is included as long as it falls within the range when measured based on Hammett's rule.

Specific examples of R ₁ , R ₂ and R ₃ which are electron withdrawing groups having a σ _p value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Cyano group, nitro group, dialkylphosphono group, diarphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiol group Carbonyl group, halogenated alkyl group, halogenated alkoxy group,
A halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, a heterocyclic group,
Examples thereof include a halogen atom, an azo group, and a selenocyanate group. Among these substituents, the group capable of further having a substituent may further have a substituent as mentioned below for R ₄ .

R ₁ , R ₂ and R ₃ will be described in more detail. As the electron-withdrawing group having a σ _p value of 0.20 or more, an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4- Dodecyloxybenzoyl), acyloxy group (eg acetoxy), carbamoyl group (eg carbamoyl, N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N- (4-n-pentadecanamide) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, iso-
Propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl, perfluorohexylethoxycarbonyl, 2-
Decyl-hexyloxycarbonylmethoxycarbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl, 2,5-di-t-amylphenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (for example, dimethylphosphono), Diarylphosphono group (for example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl), alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), arylsulfinyl group (for example, 3-pentadecylphenyl) Sulfinyl), alkylsulfonyl group (for example, methanesulfonyl, octanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, Toluene sulfonyloxy)
Acylthio group (eg, acetylthio, benzoylthio), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl), N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), halogenated alkyl group ( For example, trifluoromethyl, heptafluoropropyl), halogenated alkoxy groups (eg trifluoromethyloxy), halogenated aryloxy groups (eg pentafluorophenyloxy),
Halogenated alkylamino group (for example, N, N-di-
(Trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,1,2,2-
Tetrafluoroethylthio), an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more (for example, 2,
4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-
Benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl), halogen atom (for example, chlorine atom, bromine atom), azo group (for example, phenylazo) or Represents a selenocyanate group.

Typical σ _p values of electron-withdrawing groups are cyano group (0.66), nitro group (0.78), trifluoromethyl group (0.54), acetyl group (0. 5
0), trifluoromethanesulfonyl (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

Preferred as R ₁ , R ₂ and R ₃ are an acyl group, an acyloxy group, a carbamoyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group, Mention may be made of halogenated aryloxy groups, halogenated aryl groups, aryl groups substituted with two or more nitro groups, and heterocyclic groups. More preferably,
An acyl group, an alkoxycarbonyl group, an aryloxycarbonyl, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group.
More preferably, a cyano group, an alkoxycarbonyl group,
Aryloxycarbonyl and halogenated alkyl groups. Particularly preferably, a cyano group, a fluorine atom, an alkoxycarbonyl group substituted with an alkoxycarbonyl group or a carbamoyl group, an alkoxycarbonyl group having a linear, branched or ether bond, unsubstituted or substituted with an alkyl group or an alkoxy group It is an aryloxycarbonyl group. As a combination of R ₁ and R ₂ , preferably, R ₁ is a cyano group and R ₂ is an alkoxycarbonyl group substituted by a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, or a linear, branched or ether bond-containing alkoxycarbonyl group. It is an aryloxycarbonyl group which is substituted with a group, unsubstituted or an alkyl group or an alkoxy group.

R ₄ represents a hydrogen atom or a substituent (including an atom), and the substituent is a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, Alkyl / aryl or heterocyclic thio group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkenyloxy group, formyl group, Alkyl / aryl or heterocyclic acyl group, alkyl / aryl or heterocyclic sulfonyl group,
Alkyl / aryl or heterocyclic sulfinyl group, alkyl / aryl or heterocyclic oxycarbonyl group,
Alkyl / aryl or heterocyclic oxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, phosphonyl group, sulfamide group, imide group,
Azolyl group, hydroxy group, cyano group, carboxy group,
Examples thereof include a nitro group, a sulfo group and an unsubstituted amino group. The alkyl group, aryl group or heterocyclic group contained in these groups may be further substituted with the substituents exemplified for R ₄ .

More specifically, R ₄ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an aliphatic group (eg, a straight chain or branched chain alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), an aryl group (preferably having 6 to 36 carbon atoms, for example, phenyl, naphthyl, 4-hexadecoxyphenyl,
4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, 3- (2,4
-Di-t-amylphenoxyacetamido) phenyl), a heterocyclic group (eg 3-pyridyl, 2-furyl, 2
-Thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), alkoxy groups (eg methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2 -Methylphenoxy, 4
-Tert-butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), heterocycle An oxy group (for example, 2-benzimidazolyloxy, 1-phenyltetrazole-5-oxy,
2-tetrahydropyranyloxy), an alkyl aryl or a heterocyclic thio group (eg methylthio, ethylthio, octylthio, tetradodecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4
-Tert-butylphenoxy) propylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio,
3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,4-triazole-6-thio, 2-pyridylthio), acyloxy group (eg acetoxy, hexadecanoyloxy), carbamoyloxy group (eg N-ethylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (eg trimethylsilyl) Oxy, dibutylmethylsilyloxy), a sulfonyloxy group (for example, dodecylsulfonyloxy), an acylamino group (for example, acetamide, benzamide, tetradecanamide, (2,4-di-t-amylphenoxyacetamide, 2- [4- (4- (Hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide) Alkylamino group (e.g. methylamino, butylamino, dodecylamino, dimethylamino, diethylamino, methylbutylamino), an arylamino group (e.g. phenyl amino, 2-chloroanilino, 2-chloro-5-tetradecaneamido anilino,
N-acetylanilino, 2-chloro-5- [α-2-te
rt-Butyl-4-hydroxyphenoxy) dodecanamide] anilino, 2-chloro-5-dodecyloxycarbonylanilino), a ureido group (eg, methylureido,
Phenylureido, N, N-dibutylureido, dimethylureido), sulfamoylamino group (eg N, N
-Dipropylsulfamoylamino, N-methyl-N-
Decylsulfamoylamino), alkenyloxy group (eg 2-propenyloxy), formyl group, alkyl aryl or heterocyclic acyl group (eg acetyl, benzoyl, 2,4-di-tert-amylphenylacetyl, 3-phenyl) Propanoyl, 4-dodecyloxybenzoyl), alkyl aryl or heterocyclic sulfonyl group (eg methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl group (eg octansulphinyl, dodecylsulfinyl, dodecanesulfinyl, dodecanesulfinyl, phenyl) Sulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), an alkyl aryl or a heterocyclic oxycarbonyl group (eg methoxy) Cycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), an alkyl aryl or a heterocyclic oxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino,
Phenoxycarbonylamino, 2,4-di-tert-butylphenoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5) -Tert-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N- Ethyl- -Dodecylsulfamoyl, N, N-diethylsulfamoyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), sulfamide group (eg dipropylsulfamoylamino), imide group (eg N -Succinimide, hydantoinyl, N-phthalimide, 3-octadecenylsuccinimide), azolyl group (eg imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy group, cyano group, carboxy group, nitro group , A sulfo group, and an unsubstituted amino group.

R ₄ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino. Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Examples thereof include sulfinyl group, phosphonyl group, acyl group and azolyl group. More preferably an alkyl group or an aryl group, more preferably at least one alkoxy group, a sulfonyl group, a sulfamoyl group,
It is an alkyl group or an aryl group having a carbamoyl group, an acylamide group or a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent.

In the general formula (Ia), X represents a hydrogen atom or a group which is split off when the coupler reacts with an oxidant of an aromatic primary amine color developing agent (hereinafter, simply referred to as "leaving group"). When X represents a leaving group, the leaving group is a halogen atom, an aromatic azo group, oxygen / nitrogen /
Alkyl group, aryl group or heterocyclic group, alkyl or arylsulfonyl group, arylsulfinyl group, alkyl-aryl or heterocyclic carbonyl group that binds to a coupling position via a sulfur or carbon atom, or a coupling position at a nitrogen atom Which is a heterocyclic group, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or aryl sulfonyloxy group, an acylamino group, an alkyl or aryl sulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, Alkyl
Aryl or heterocyclic thio group, carbamoylamino group, arylsulfonyl group, arylsulfonyl group,
There are 5- or 6-membered nitrogen-containing heterocyclic groups, imide groups, arylazo groups, etc., and the alkyl group, aryl group or heterocyclic group contained in these leaving groups is further substituted with the substituent at R _4. When two or more of these substituents are present, they may be the same or different, and these substituents may further have the substituents mentioned for R ₄ .

More specifically, the leaving group is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonyl). Methoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), an acyloxy group ( For example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino (E.g., di-chloroacetyl amino, heptafluorobutyryl amino), alkyl or aryl sulfonamido group (e.g., methanesulfonic amino, trifluoromethanesulfonic amino, p
-Toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy),
Alkyl / aryl or heterocyclic thio groups (eg,
Ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), arylsulfonyl group (for example, 2-butoxy-5-tert-octylphenylsulfonyl), arylsulfinyl group (for example, 2-butoxy-5-tert-
Octylphenylsulfinyl), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2- Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. Of course, these groups may be further substituted with the groups listed as the substituent for R ₄ . Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. . More preferably, it is an arylthio group.

In the cyan coupler represented by the general formula (Ia), the group represented by R ₁ , R ₂ , R ₃ , R ₄ or X is represented by the general formula (I).
a) containing a cyan coupler residue represented by a) to form a dimer or higher multimer, R ₁ , R ₂ ,
The R ₃ , R ₄ or X group may contain a polymer chain to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is represented by the general formula (I
A typical example is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a cyan coupler residue represented by a). In this case, one or more kinds of cyan color-forming repeating units having a cyan coupler residue represented by the general formula (Ia) may be contained in the polymer, and acrylic acid ester, methacrylic acid ester, maleic acid are used as copolymerization components. It may be a copolymer containing one or more non-color-forming ethylene type monomers that do not couple with the oxidation products of aromatic primary amine developers such as esters. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0027]

[Chemical 8]

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Chemical 11]

[0031]

[Chemical 12]

[0032]

[Chemical 13]

[0033]

[Chemical 14]

[0034]

[Chemical 15]

[0035]

[Chemical 16]

[0036]

[Chemical 17]

The compound of the present invention and its intermediate can be synthesized by a known method. For example, J. Am. Chem. Soc., 80, 5332 (1958), J. Am.
Am. Chem., 81, 2452 (1959), J. Am. Chem.
Soc., 112, 2465 (1990), Org.Synth., I
270 (1941), J. Chem. Soc., 5149 (196).
2), Hetrocyclic., 27, 2301 (1988),
Rec.Trav.chim., 80, 1075 (1961) and the like, or the literature cited therein or a similar method. Next, a specific synthesis example will be shown. (Synthesis Example 1) Synthesis of Exemplified Compound (9) Exemplified Compound (9) was synthesized by the following route.

[0038]

[Chemical 18]

2-Amino-4-cyano-3-ethoxycarbonylpyrrole (1a) (66.0 g, 0.4 mol)
In dimethylacetamide (300 ml) at room temperature, 3,5-dichlorobenzoyl chloride (2a) (8
3.2 g, 0.4 mol) is added and stirred for 30 minutes. Add water and extract twice with ethyl acetate. The organic layers are combined, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and acetonitrile (300 ml)
When recrystallized from compound (3a) (113 g, 84
%) Was obtained.

A powder of potassium hydroxide (252 g, 4.5 mol) was added to a solution of (3a) (101.1 g, 0.3 mol) in dimethylformamide (200 ml) at room temperature and stirred well. While cooling with water, hydroxylamine-O-sulfonic acid (237 g, 2.1 mol) was added little by little, taking care not to raise the temperature rapidly, and the mixture was stirred for 30 minutes after addition. A 0.1N hydrochloric acid aqueous solution is added dropwise to neutralize while observing the pH test paper. Extract three times with ethyl acetate, wash the organic layer with water and saturated brine, and dry over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent, hexane: ethyl acetate = 2: 1) to give compound (4a) (9.50 g, 9%).

Carbon tetrachloride (9c) was added to a solution of (4a) (7.04g, 20mmol) in acetonitrile (30ml) at room temperature.
c) is added, followed by triphenylphosphine (5.76).
g, 22 mmol) and heated to reflux for 8 hours. After cooling, water is added and the mixture is extracted 3 times with ethyl acetate. The organic layer is washed with water and saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 4: 1) to obtain (5a) (1.13 g, 17%).

1.8 g of the obtained (5a) and 12.4 g of (6a) were dissolved in 2.0 ml of sulfolane, and further 1.5 g was dissolved.
Of titanium isopropoxide was added. After keeping the reaction temperature at 110 ° C. and reacting for 1.5 hours, ethyl acetate was added and the mixture was washed with water. The ethyl acetate layer was dried, evaporated, and purified by residue column chromatography to obtain 1.6 g of the desired exemplary compound (9). Melting point is 9
It was 7-98 degreeC.

The compound represented by the general formula (Ia) of the present invention is 2.0 to 1.0 × 10 per mol of silver halide.
It can be used in the range of ^-3 mol. Preferably 1.
0 to 2.0 × 10 ⁻² mol, more preferably 5.0
It is in the range of × 10 ^{-1 to} 5.0 × 10 ^-2 mol.

In the present invention, when the compound represented by formula (Ia) is used as the main coupler, it is preferably added to the red-sensitive silver halide emulsion layer or the non-photosensitive layer adjacent thereto. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer according to the purpose.

In the present invention, the compounds represented by the general formula (Ia) can be used in combination of two or more kinds. Also,
It can be used alone in multiple layers. In the present invention, the cyan coupler represented by the general formula (II) or the general formula (III) described later is used in the same light-sensitive material, but in the present invention, it may be used in combination with other known cyan couplers.

In the present invention, the compound represented by the general formula (Ia) is represented by the general formula (II) or the general formula (III) described later.
It can be introduced into the color light-sensitive material by various known dispersion methods including the couplers of

In the present invention, the compound represented by the general formula (Ia) is preferably an oil-in-water dispersion method in which the compound including the coupler of the general formula (II) or the general formula (III) is dispersed using a high boiling point organic solvent. As the high-boiling organic solvent, those having a boiling point of 175 ° C. or higher at normal pressure are preferable, and the amount thereof is 5.0 cc or less per 1 g of the compound of the general formula (Ia), preferably 1 × 10 ⁻³ It is 2.0 cc, more preferably 1 × 10 ^{-2 to} 1.0 cc.

Next, the compound represented by formula (II) will be described in detail. R ₁ is -CONR ₄ R ₅ , -S
_{O 2 NR 4 R 5, -NHCOR} 4, NHCOOR 6, -
NHSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHS
Representing O ₂ NR ₄ R ₅ , R ₄ R ₅ and R ₆ are each independently an alkyl group having 1 to 30 total carbon atoms (hereinafter referred to as C number), an aryl group having 6 to 30 C atoms, or 2 to C numbers. Thirty
Represents a heterocyclic group. R ₄ and R ₅ may also be hydrogen atoms.

R ₂ represents a group capable of substituting on a naphthalene ring (including atoms; the same applies hereinafter), and representative examples thereof include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carbonyl group, an amino group and a sulfo group. , Cyano group, alkyl group, aryl group, heterocyclic group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, Examples thereof include an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group and an imide group. Examples of when k = 2 include a dioxymethylene group and a trimethylene group.
The C number of (R ₂ ) _k is 0 to 30.

R ₃ represents a substituent, preferably represented by the following formula (II-1). Formula (II-1) R ₇ (Y) _m − In formula (II-1), Y is>NH,> CO or> SO.
₂ , m is an integer of 0 or 1, R ₇ is a hydrogen atom, a C 1-30 alkyl group, a C 6-30 aryl group, C
Number 2 to 30 heterocyclic group, -COR ₈

[0051]

[Chemical 19]

Or —SO ₂ R ₁₀ respectively. Here, R ₈ , R ₉ and R ₁₀ have the same meanings as R ₄ , R ₅ and R ₆ , respectively. In R ₁ or R ₇ , -N
R _{4 and} R ₅ of R ₄ R ₅ and R ₈ and R ₉ of —NR ₈ R ₉ may be bonded to each other to form a nitrogen-containing heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring).

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer (referred to as a leaving group, including a leaving atom, the same applies hereinafter), and a typical example of the leaving group. As a halogen atom,

[0054]

[Chemical 20]

A thiocyanate group and a heterocyclic group having a C number of 1 to 30 and bonded to a coupling active position at a nitrogen atom (eg, succinimide group, phthalimido group, pyrazolyl group, hydantoinyl group, 2-benzotriazolyl group) are used. Can be mentioned. Here, R ₁₁ has the same meaning as R ₆ .

In the above, the alkyl group may be linear, branched or cyclic, and may have a substituent (for example, a halogen atom, a hydroxyl group, an aryl group or a heterocyclic group) even if it contains an unsaturated bond. , An alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group), and representative examples include methyl, isopropyl, isobutyl, t-butyl, 2- Ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3- (2,4-di-
There is t-pentylphenoxy) propyl.

Even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
A cyano group, an acyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group), phenyl as a representative example,
Tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2
-Tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, 4-t-butylphenyl.

The heterocyclic group is O, N, S, P, Se, T
a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one hetero atom of e in the ring, which is a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group,
Nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), As typical examples, 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
There are 1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl and 5-methyl-1,3,4-oxadiazol-2-yl.

Examples of preferable substituents in the present invention will be described below. R ₁ is -CONR ₄ R ₅ or -SO
₂ NR ₄ R ₅ is preferable, and specific examples include carbamoyl,
N-n-butylcarbamoyl, Nn-dodecylcarbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3
-(2,4-di-t-pentylphenoxy) propyl]
Carbamoyl, N-hexadecylcarbamoyl, N-
[4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-dodecyloxy-2-methylpropyl) carbamoyl, N- [3- (4-t-octylphenoxy) propyl] carbamoyl , N-hexadecyl-N-methylcarbamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N- [4- (2,
4-di-t-pentylphenoxy) butyl] sulfamoyl. R ₁ is particularly preferably -CONR ₄ R ₅ .

As R ₂ and k, k = 0, that is, unsubstituted one is most preferable, and then k = 1 is preferable. R ₂ is preferably a halogen atom, an alkyl group (eg, methyl,
It is isopropyl, t-butyl, cyclopentyl), a carbonamide group (eg acetamide, pivalinamide, trifluoroacetamide, benzamide), a sulfonamide (eg methanesulfonamide, toluenesulfonamide) or a cyano group.

R ₃ is preferably m in formula (II-1).
= 0, more preferably R ₇ is —COR ₈ [eg formyl, acetyl, trifluoroacetyl, 2-
Ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4- (2,4-di-t-pentylphenoxy) butanoyl], -COOR ₁₀ [eg methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-
Dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or —SO ₂ R ₁₀ [eg methylsulfonyl, n-butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, p-
Chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably R ₇ is —COOR ₁₀ .

X is preferably a hydrogen atom, a halogen atom,
-OR ₁₁ [eg ethoxy, 2-hydroxyethoxy,
2-methoxyethoxy, 2- (2-hydroxyethoxy) ethoxy, 2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N- (2-methoxyethyl) carbamoylmethoxy, 1-carboxytridecyloxy. Two
An alkoxy group such as methanesulfonamidoethoxy, 2- (carboxymethylthio) ethoxy, 2- (1-carboxytridecylthio] ethoxy, eg 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t -Octylphenoxy, 4-nitrophenoxy, 4- (3-carboxypropanamide)
Phenoxy, aryloxy groups such as 4-acetamidophenoxy group] or -SR ₁₁ [eg carboxymethylthio, 2-carboxymethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2- (N An alkylthio group such as -N-dimethylamino) ethylthio, such as 4-carboxyphenylthio, 4-methoxyphenylthio, 4
An arylthio group such as-(3-carboxypropanamide) phenylthio], and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

The coupler represented by the general formula (II) may form a bis form in the substituents R ₁ , R ₂ , R ₃ or X, each of which is bound to each other via a divalent or divalent or more divalent group. Multimers or higher multimers may be formed. In this case, the carbon number range shown in each of the above substituents may be out of the range. When the coupler represented by the general formula (II) forms a multimer, an addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (a homopolymer or a copolymer of a cyan color-forming monomer is a typical example, preferably . equation represented by the formula (II-2) is (II-2) - (G i) gi - (H j) hj - in formula (II-2) G _i is a repeating unit derived from the color forming monomers Is a group represented by formula (II-3), H _j is a repeating unit derived from a non-color-forming monomer and is a group represented by formula (II-3), i is a positive integer, and j is Represents 0 or a positive integer, and gi and hi respectively represent the weight fraction of G _I or H _j , where when i or j is plural, G _i or H _j contains plural kinds of repeating units. Formula (II-3)

[0064]

[Chemical 21]

In the formula (II-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A
Represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a divalent group having carbon atoms below both such as a substituted or unsubstituted alkylene group, a phenylene group or an oxydialkylene group. And L is-
CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-,-
OCO -, - CO -, - O -, - SO 2 -, NHSO 2
-, or represents a -SO ₂ NH-. a, b, and c represent an integer of 0 or 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ , R ₂ , R ₃ or X of the compound represented by the general formula (II).

As the non-color-forming, ethylene-type monomer which does not couple with the oxidation product of the aromatic primary amine developing agent which gives the repeating unit H _j , acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid Amides or esters derived from these acrylic acids (eg, methacrylic acid) (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methac And β-hydroxyethyl methacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinyl). Acetophenone and sulfostyrene), itaconic acid, citraconic acid,
Examples include crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerizing with the vinyl monomer corresponding to the above formula (II-3) is in the form of the copolymer to be formed, for example, solid. , Liquid, micelles and physical and / or chemical substances such as solubility (solubility in water or organic solvents), compatibility with photographic colloid composition binders such as gelatin, its flexibility , Thermal stability, coupling reactivity with an oxidized product of a developing agent, and diffusion resistance in a photographic colloid can be favorably influenced. These copolymers may be random copolymers or copolymers having a specific sequence (for example, block copolymer, alternating copolymer).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of several thousands to several millions, but oligomeric polymer couplers of 5000 or less can also be used. The cyan polymer coupler used in the present invention is an organic solvent (for example, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone,
Whether it is a lipophilic polymer soluble in dibutyl phthalate or tricresyl phosphate) or a hydrophilic polymer miscible with a hydrocolloid such as gelatin aqueous solution, it has a structure and properties capable of forming micelles in the hydrocolloid. It may be a polymer.

In order to obtain a lipophilic polymer coupler which is soluble in an organic solvent, a lipophilic non-color forming ethylenic monomer (eg acrylic acid ester, methacrylic acid ester, maleic acid ester, vinylbenzenes etc.) is mainly used as a copolymerization component. Is preferred. The general formula (II-
It may be prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by 3) in an organic solvent and emulsifying and dispersing it in an aqueous gelatin solution in the form of latex. It may be prepared by an emulsion polymerization method.

A method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. 370,952
The method described in the publication can be used. Alternatively, in order to obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-2-sulfonateethyl) acrylamide, 3-sulfonatepropylacrylate, sodium styrenesulfonate, Styrene potassium sulfinate, acrylamide,
It is preferable to use a hydrophilic non-color forming ethylene-like monomer such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine, etc. as the copolymer component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and a water-miscible organic solvent such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide and dimethylacetamide. It can also be dissolved in a mixed solvent of water and water and added. Furthermore, it may be added after being dissolved in an alkaline aqueous solution or an organic solvent containing alkaline water. Also, a small amount of surfactant may be added.

Specific examples of each substituent in the formula (II) and the cyan coupler represented by the formula (II) are shown below.

Example of R ₁

[Chemical formula 22]

[0075]

[Chemical formula 23]

[0076]

[Chemical formula 24]

[0077]

[Chemical 25]

Examples of R ₂

[Chemical formula 26]

Examples of R ₃ NH-

[Chemical 27]

[0080]

[Chemical 28]

[0081]

[Chemical 29]

[0082]

[Chemical 30]

[0083]

[Chemical 31]

Example of X

[Chemical 32]

[0085]

[Chemical 33]

[0086]

[Chemical 34]

[0087]

[Chemical 35]

Specific examples of the cyan coupler represented by the general formula (II)

[Chemical 36]

[0089]

[Chemical 37]

[0090]

[Chemical 38]

[0091]

[Chemical Formula 39]

[0092]

[Chemical 40]

[0093]

[Chemical 41]

[0094]

[Chemical 42]

[0095]

[Chemical 43]

Specific examples of the cyan coupler represented by the formula (II) other than the above and / or methods for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889, JP-A-60.
-237448, 61-153640, 61-
No. 145557, No. 63-208042, No. 64-3
1159 and West German Patent No. 3823049A. The cyan coupler represented by the formula (II) is
As described in JP-A-62-269958,
It is preferable to use a small amount of a high boiling point organic solvent for dispersion in order to further improve the sharpness and desilvering property.

Specifically, the high boiling point organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less with respect to the cyan coupler represented by the formula (II). The cyan coupler represented by the formula (II) is preferably used in combination of two or more kinds. When the same color sensitivity is divided into two or more layers having different sensitivities, a 2-equivalent cyan coupler is used in the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use either or both of the same color-sensitive layers other than those.

Next, the phenolic cyan coupler represented by the general formula (III) will be described in detail below. In the general formula (III), R ¹ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 36 (preferably 4 to 30) total carbon atoms (hereinafter referred to as C number),
An optionally substituted aryl group having a C number of 6 to 36 (preferably 12 to 30) or a C number of 2 to 36 (preferably 1)
2 to 30) is represented. Here, the heterocyclic group represents a 5 to 7-membered optionally condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring, and examples As 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl,
There are 2-imidazolyl, 4-quinolyl and the like. Examples of the substituent of R ¹ include a halogen atom, a cyano group, a nitro group,
Carboxyl group, sulfo group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, imide group, amino Group, ureido group, alkoxylcarbonylamino group or sulfamoylamino group (hereinafter referred to as substituent group A),
Examples of preferable substituents are an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group or an imido group.

In the general formula (III), R ² has a C number of 6 to 36.
It represents an aryl group (preferably 6 to 15) and may be substituted with a substituent selected from the above-mentioned Substituent group A or may be a condensed ring. Here, as a preferable substituent, a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, benzoyl), an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloro). Methyl), alkoxy groups (eg methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (eg methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (eg phenylsulfonyl, p-tolylsulfonyl, p). -Chlorophenylsulfonyl), an alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), a sulfonamide group (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), Bamoiru group (e.g. N, N- dimethylcarbamoyl, N- phenylcarbamoyl), or a sulfamoyl group (e.g. N, N
-Diethylsulfamoyl, N-phenylsulfamoyl). R ³ is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy- 4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4- Trifluoromethylphenyl or 3-sulfon A Dofeniru, particularly preferably 4-cyanophenyl, 3-cyano -
4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (III), Z represents a hydrogen atom or a coupling-off group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Examples of coupling-off groups include halogen atoms, sulfo groups,
An alkoxy group having a C number of 1 to 36 (preferably 1 to 24),
An aryloxy group having a C number of 6 to 36 (preferably 6 to 24), an acyloxy group having a C number of 2 to 36 (preferably 2 to 24), an alkylsulfonyl group having a C number of 1 to 36 (preferably 1 to 24), Arylsulfonyl group having a C number of 6 to 36 (preferably 6 to 24), C number of 1 to 36 (preferably 2 to)
24) alkylthio group, C number of 6 to 36 (preferably 6)
To 24) arylthio group, C number of 4 to 36 (preferably 4 to 24) imide group, C number of 1 to 36 (preferably 1 to 36)
24) a carbamoyloxy group or a heterocyclic group bonded to the coupling active position with a nitrogen atom having a C number of 1 to 36 (preferably 2 to 24) (eg pyrazolyl, imidazolyl,
1,2,4-triazol-1-yl, tetrazolyl)
There is. Here, the following groups are the alkoxy groups A
It may be substituted with a substituent selected from Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group thio group, and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an aryloxy group.

Specific examples of R ¹ , R ² and Z in the general formula (III) are shown below.

Examples of R ¹

[Chemical 44]

[0103]

[Chemical formula 45]

[0104]

[Chemical formula 46]

[0105]

[Chemical 47]

[0106]

[Chemical 48]

[0107]

[Chemical 49]

[0108]

[Chemical 50]

Examples of R ²

[Chemical 51]

[0110]

[Chemical 52]

Example of Z

[Chemical 53]

[0112]

[Chemical 54]

[0113]

[Chemical 55]

[0114]

[Chemical 56]

Specific examples of the cyan coupler represented by the general formula (III) are shown below. However, A to Z and a to f are
4, Chemical 45, Chemical 46, Chemical 47, Chemical 48, Chemical 49, Chemical 50
It is a serial number of a specific example of R ¹ in.

[0116]

[Table 1]

[0117]

[Table 2]

[0118]

[Table 3]

[0119]

[Table 4]

[0120]

[Table 5]

The cyan coupler represented by the general formula (III) is described in, for example, JP-A-56-65134 and JP-A-61-2757.
No. 63-159848, No. 63-161450.
No. 63-161451, JP-A No. 1-254956.
No. 4,923,791, and US Pat. No. 4,923,791.

In the present invention, the cyan coupler represented by the general formula (Ia) and the cyan coupler represented by the general formula (II) or the general formula (III) are used in combination. Formula (II) or general formula (I
The ratio of II) can be set arbitrarily. That is, the general formula (I
a): General formula (II) or (III) is 99.9: 0.1
It can be taken in a ratio of 0.1: 99.9 (molar ratio). The ratio of the general formula (Ia) / total cyan coupler is preferably 30 mol% or more, more preferably 50 mol% or more, and the upper limit value is 99.9 mol%. In the present invention, the total amount of the coupler represented by the general formula (Ia) and the general formula (II) or the general formula (III) in the photosensitive material is 1 mol of silver halide when used in the photosensitive layer. 1 × 10 ^-3 per
It is in the range of 2 moles. It is preferably in the range of 1 × 10 ^-2 to 1 mol, and more preferably in the range of 2 × 10 ^{-2 to} 0.5 mol. When used in the non-photosensitive layer, it is in the range of 1 × 10 ⁻³ to 1 mol per mol of silver halide in the adjacent photosensitive layer. The amount is preferably 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 5 × 10 ⁻³ to 2 × 10 ⁻¹ mol. The total coating amount of the coupler represented by the general formula (Ia) and the general formula (II) or the general formula (III) is 1
The range is 1 × 10 ^{−3 to 3} g / m ² per layer. It is preferably 5 × 10 ^{−3 to 1} g / m ² , and more preferably 1 × 10.
^There is a range of ^{−2 to} 5 × 10 ⁻¹ g / m ² .

The couplers represented by the general formula (Ia) and the general formula (II) or the general formula (III) of the present invention can be introduced into the light-sensitive material by any known dispersion method. However, a method of adding a dispersion using an oil-in-water dispersion method described below is preferable.

In the present invention, by using the cyan coupler represented by the general formula (Ia) and the cyan coupler represented by the general formula (II) or the general formula (III), the cyan coupler represented by the general formula (Ia) can be obtained. In addition to maintaining the high color development and color image fastness of cyan couplers, it also improves the quality and brings about the effect of reducing fluctuations in photographic properties due to fluctuations in color development processing, and is stable in color developing solutions with high bromine ion concentrations. The processability is shown.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- 89850, it is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, RL, adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(November 1979), p. 648, ibid. No. 307105 (November 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Brightening agent: page 24, page 647, right column 868, fogging prevention 24: 25, page 649, right column 868: 870, stabilizer: light absorber, 25: Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 left column 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. As the cyan coupler, in addition to the couplers represented by the general formula (Ia), the general formula (II) and the general formula (III), there are disclosed in JP-A-64-553, 64-554 and 64-5.
55 and 64-556, pyrazoloazole couplers, imidazole couplers described in U.S. Pat.No. 4,818,672, 3-hydroxypyridine cyan couplers described in European Patent EP0,333,185A2 (among others, The coupler (42) listed as an example is a 4-equivalent coupler having a chlorine-releasing group to make it a 2-equivalent compound, and couplers (6) and (9) are particularly preferable) and JP-A-64-32260. And a cyclic active methylene cyan coupler (among others, coupler examples 3, 8, and 34 listed as specific examples are particularly preferable). Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,211.
No. 4,367,282, 4,409,320, 4,57
6,910, British Patent 2,102,137, European Patent 341,188
It is described in No. A, etc.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains. The effect is great when it is added to the photosensitive material using. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,1
No. 40, No. 2,131,188, JP-A Nos. 59-157638 and 59-1.
Those described in No. 70840 are preferable. In addition, JP-A-60-10
7029, 60-252340, JP-A-1-44940, 1-456
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 87 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 19, No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after treatment for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

Color development processing of the light-sensitive material of the present invention will be described below. The color photographic light-sensitive material according to the present invention comprises
The RD. No.17643, pages 28-29, No.18716, 651 left column-right column, and No. 307105, No. 307-8, pages 880-881 can be developed by the usual method,
In the present invention, the color developing solution used for the developing treatment is a color developing solution having a bromine ion concentration of 1.30 × 10 ^-2 mol / liter or more. Bromine ion concentration 1.30 × 10 ^-2 mol /
In the present invention, bromine ions may be added directly to the color developing solution in order to maintain the liter or more, or may be eluted from the light-sensitive material being processed. When directly added to the color developing solution, the bromine ion supplying substance may be an inorganic substance or an organic substance as long as it is a compound capable of becoming a bromine ion in the color developing solution. Preferred are inorganic compounds such as sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, odor. Although thallium bromide and the like can be mentioned, of these, preferred compounds are potassium bromide and sodium bromide. When it is eluted from the light-sensitive material being processed and supplied, it may be supplied from a silver halide emulsion containing silver bromide or an additive other than the silver halide emulsion. In the present invention, the bromine ion concentration is 1.30 × 10 ^-2 mol / liter or more, more preferably 1.50 × 10 ^-2 mol / liter or more, and the upper limit value is in the range of 6.0 × 10 ^-2 mol / liter. Is. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples thereof include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include an inhibitor or an antifoggant. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N- tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
For the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
May, May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society edited, "Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit the effect when applied to the lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0145]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: gelatin hardener ExS: amount sensitizing dye coating amount which represents the amount for silver halide and colloidal silver were represented in units of g / m ² of silver and coupler, for additives and gelatin in the unit of g / m ² For the sensitizing dye, the number of moles per mole of silver halide in the same layer is shown.

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 1.90 ExM-1 2.0 × 10 ^-2 HBS-1 3.0 × 10 ^-2

Second layer (intermediate layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 HBS-2 7.0 × 10 ^-2

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.15 Emulsion B Silver 0.25 Gelatin 0.90 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 Comparative coupler (1) 0.19 ExC-2 3.0 x 10 ^-2 ExC-4 1.0 x 10 ^-2 Cpd-12 0.12 HBS-1 7.0 x 10 ^-3 HBS-4 3.0 x 10 ^-3

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.25 Emulsion D Silver 0.45 Gelatin 1.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 Comparative coupler (1) 0.28 ExC-1 8.0 × 10 ^-2 ExC-3 2.0 × 10 ^-2 ExC-4 1.5 × 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-10 1.0 × 10 ^-4 Cpd-12 0.10 HBS- 1 7.0 x 10 ^-2 HBS-3 3.0 x 10 ^-2

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 0.60 Gelatin 0.80 ExS-1 1.2 × 10 ^-4 ExS-2 3.5 × 10 ^-4 ExS-3 1.2 × 10 ^-5 Comparative coupler (1) 7.0 × 10 ^-2 Comparative coupler (2) 8.0 × 10 ^-2 ExC-3 1.0 × 10 ^-2 ExC-4 1.5 × 10 ^-2 Cpd-13 0.15 HBS-1 9.0 × 10 ^-2 HBS-2 6.0 × 10 ^-2

Sixth layer (intermediate layer) Gelatin 0.80 P-2 0.17 Cpd-1 0.15 Cpd-4 0.17 HBS-1 5.0 × 10 ^-2

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion F Silver 0.10 Emulsion G Silver 0.15 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExM- 1 3.0 × 10 ^-2 ExM-2 0.20 ExY-1 3.0 × 10 ^-2 Cpd-11 7.0 × 10 ^-3 HBS-1 0.20

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion H Silver 0.55 Gelatin 1.00 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM-1 3.0 × 10 ^{-2 ExM-2 0.25 ExM-3} 1.5 × 10 -2 ExY-5 4.0 × 10 -2 Cpd-11 9.0 × 10 -3 Cpd-14 0.10 HBS-1 0.15 HBS-2 5.0 × 10 -2

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion I Silver 0.45 Gelatin 0.90 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 2.0 × 10 ^-5 ExS-7 3.0 × 10 ^-4 ExM-1 1.0 x 10 ^-2 ExM-4 3.9 x 10 ^-2 ExM-5 2.6 x 10 ^-2 ExY-5 0.5 x 10 ^-2 Cpd-2 1.0 x 10 ^-2 Cpd-9 2.0 x 10 ^-4 Cpd-10 2.0 x 10 ^-4 Cpd-13 0.10 HBS-1 0.10 HBS-3 5.0 x 10 ^-2

10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 HBS-1 0.15

[0157] 11th layer (low sensitivity blue-sensitive emulsion layer) Emulsion J silver 0.10 Emulsion K silver 0.20 Gelatin ^{1.30 ExS-8 2.0 × 10 -4} ExC-3 3.0 × 10 -2 ExY-1 6.0 × 10 -2 ExY- 3 0.45 ExY-4 0.40 Cpd-2 1.0 × 10 ^-2 Cpd-13 0.20 HBS-1 0.20 HBS-4 0.10

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion L Silver 0.40 Gelatin 0.60 ExS-8 1.0 × 10 ⁻⁴ ExY-3 6.0 × 10 ⁻² ExY-4 5.0 × 10 ⁻² ExY-5 0.5 × 10 ^-2 Cpd-2 1.0 x 10 ^-3 Cpd-12 4.0 x 10 ^-2 HBS-1 4.0 x 10 ^-2

Thirteenth Layer (First Protective Layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.20 Gelatin 0.80 UV-2 0.10 UV-3 0.10 UV-4 0.20 HBS-3 4.0 × 10 ^-2 P-3 9.0 x 10 ^-2

14th layer (second protective layer) Gelatin 0.90 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40

Furthermore, storability, processability, pressure resistance, anti-mold and
In order to improve antibacterial properties, antistatic properties, and coating properties, the following Cpd-3, Cpd-5 to Cpd-8, P-
1, P-2, W-1 to W-3 were added. In addition to the above, B-4, F-1 to F-11, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, and a rhodium salt are appropriately contained in each layer. Next, a list of emulsions used in the present invention and the chemical structural formulas or chemical names of the compounds are shown below.

[0162]

[Table 6]

[0163]

[Table 7]

In Tables 6 and 7, (1) each emulsion was reduction-sensitized at the time of grain preparation with thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of Japanese Patent Application No. 2-34090. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0165]

[Chemical 57]

[0166]

[Chemical 58]

[0167]

[Chemical 59]

[0168]

[Chemical 60]

[0169]

[Chemical formula 61]

[0170]

[Chemical formula 62]

[0171]

[Chemical formula 63]

[0172]

[Chemical 64]

[0173]

[Chemical 65]

[0174]

[Chemical formula 66]

[0175]

[Chemical formula 67]

[0176]

[Chemical 68]

[0177]

[Chemical 69]

[0178]

[Chemical 70]

[0179]

[Chemical 71]

[0180]

[Chemical 72]

Samples 102 to 124 were prepared by replacing the comparative couplers (1) to (3) used in the third to fifth red-sensitive emulsion layers with the couplers shown in Table 8 in equimolar amounts. These samples 101 to 124 were subjected to the following color development processing.

The processing of the sample for evaluating the performance was performed by separately subjecting the sample to imagewise exposure until the cumulative replenishment amount of the color developing solution was replenished by 3 times the tank volume. And the treatment was carried out after continuous treatment. The treatment process and the treatment liquid composition are shown below.

(Processing step A) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 10 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3.5 liters Stability (1) 20 seconds 38.0 ℃ −3 liters Stability (2) 20 seconds 38.0 ℃ 560 milliliters 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process were each per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer A) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphospho 3.3 3.3 Acid sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Iodide Potassium 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid Ferric acid Ammo 130 195 N-monohydrate Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (PH 7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 ml 840 ml (700 g / l) Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 1.0 liter 1.0 liter pH by adding water [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common for tank liquid and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The above color development processing was carried out and the following performances were examined. (1) Gradation exposure of photographic white light (color temperature of light source 4800 ° K)
The cyan density of the color-developed sample was measured, and the logarithm of the reciprocal of the exposure amount giving the density of the minimum density + 0.3 was calculated from the characteristic curve, and this was taken as the sensitivity (S). Also,
The density at the point where an exposure amount of logE = 1.5 was read from the sensitivity point to the high exposure amount side was read, and a value obtained by subtracting the minimum density value was obtained, and this was defined as the color density (D). Regarding the sensitivity, one is to obtain a difference (ΔS ₁ ) between the sensitivity values after the continuous processing with reference to the sample 101, and the other is a sensitivity difference between the same sample before and after the continuous processing (ΔS ₁ ). S ₂ ) was determined and the processing stability was investigated. Regarding the color density, one is to obtain the density ratio (D ₁ %) of the color density value after continuous processing with reference to the sample 101.
The other was to calculate the concentration ratio (D ₂ %) between the same sample before and after continuous treatment was started. (3) Color image fastness After the gradation exposure of white light was given and the cyan density of the sample subjected to the above processing was measured with the color developing solution after continuous processing,
After storing for 30 days under the conditions of 60 ℃ and 70% relative humidity, measure the cyan density again, and obtain the minimum density before the test +1.5
The density after the test was read in terms of the exposure amount giving the density of 1., and the value obtained by subtracting the minimum density from this value was divided by 1.5 to obtain the color image residual ratio (D _C %).

The results are shown in Tables 8-11.

[0192]

[Table 8]

[0193]

[Table 9]

[0194]

[Table 10]

[0195]

[Table 11]

From Tables 8 to 11, the general formula (I
Sample 1 containing the coupler represented by a) and the coupler represented by the general formula (II) or the general formula (III) of the present invention.
It is apparent that 07 to 124 are higher in sensitivity and color density than Comparative Samples 101 to 106 and are excellent in color developability, and that the process variation of photographic property in continuous processing is small.

Example 2 The following color development processing B was carried out using the samples 101 to 124 prepared in Example 1, and the sensitivity and color density described in (1) of Example 1 were determined. The processing steps and the composition of the processing liquid are shown.

(Processing step B) Step processing time processing temperature color development 3 minutes 5 seconds 38.0 ° C bleaching 50 seconds 38.0 ° C bleach-fixing 50 seconds 38.0 ° C fixing 50 seconds 38.0 ° C water washing 30 seconds 38.0 ° C stability (1) 20 seconds 38.0 ℃ Stability (2) 20 seconds 38.0 ℃ Dry 1 minute 60 ℃

The composition of the processing liquid is shown below. (Color developer B) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphospho3.3 acid Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.43 (1.20 × 10 ^-2 ) Potassium iodide 1.3 mg Hydroxyl Amine sulfate 2.4 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 Water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit: g) 1,3-Diaminopropanetetraacetic Acid Ferric Ammonium 130 Nium Monohydrate Ammonium Bromide 80 Ammonium Nitrate 15 Hydroxyacetic Acid 50 Acetic Acid 40 Water was added to 1.0 liter pH [with ammonia water] Preparation] 4.4

(Bleaching Fixing Solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0)

(Fixer) (Unit: g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution 280 ml (700 g / liter) Imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this solution is 6.5
It was in the range of 7.5.

(Stabilizing Solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium salt of ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Subsequently, the concentration of potassium bromide in the color developing solution was changed from 1.20 × 10 ^-2 mol / liter to 1.30 × 1.
The sensitivity and the color density were determined in the same manner as described above, changing to 0 ^-2 , 1.50 x 10 ^-2 , 1.70 x 10 ^-2 mol / liter and performing the same treatments as the treatments C to E.

[0206] processing B~ process sensitivity and color density obtained by performing the E, the difference between each treatment C~ process E between the same sample No. for sensitivity to the reference processing B (△ S _BC
˜ΔS _BD , ΔS _BE ) was determined. Regarding the color density, the density ratio between the same sample No. (D _BC %, D _BD %, ΔD
_BE %) was calculated. The results are shown in Table 12.

[0207]

[Table 12]

From Table 12, samples 107 to 124 using the cyan couplers represented by the general formula (Ia) and the general formula (II) or the general formula (III) of the present invention have a bromine ion concentration in the color developing solution. 1.20 × 10 ^-2 ~ 1.70 × 10 ^-2
Even if it changes in the range of mol / liter, the processing time is lengthened, the processing temperature is raised, or the pH of the color developing solution is changed.
It can be seen that without increasing the amount of color developing agent and decreasing the amount of color developing agent, the decrease in sensitivity and color density is clearly smaller than those of Comparative Samples 101 to 106, and excellent color forming property is shown. The color image fastness was examined, but it was found that the results were almost the same as those obtained in Example 1, and that Samples 107 to 124 according to the present invention exhibited good color image fastness.

Example 3 Using the samples 101 to 124 prepared in Example 1, the replenishing amount of color development in the processing step of the color development processing used in Example 1 was 80 ml / m ² , and the color development processing temperature was 39.
C., the amount of potassium bromide in the tank composition of color developer A is 5.9.times.10.sup.- ² mol / liter, and the color developing agent 2-methyl-4- [N-ethyl-N-(. Beta.-hydroxyethyl). The amount of amino] aniline sulfate was adjusted to 8.0 g / liter, pH 10.25, and as a replenisher, 4.0 g of ethylenetriaminepentaacetic acid, 0 g of potassium bromide,
Hydroxylamine sulfate 4.8 g, color developing agent 1
Adjust the pH to 5.0g (1 liter / liter).
The value was set to 2.0 (this will be referred to as treatment F), and the photographic property was determined according to (1) described in Example 1.

The photographic properties obtained were as in Example 1.
Based on the data after completion of the continuous processing carried out in (1), the difference (ΔS _AF ) in terms of sensitivity, and the density between identical samples in terms of color density were taken for the photographic properties after the completion of continuous processing in this example. The ratio (D _AF %) was determined. The results are shown in Table 13.
Shown in.

[0211]

[Table 13]

From Table 13, samples 107 to 124 using the cyan couplers represented by the general formula (Ia) and the general formula (II) or the general formula (III) of the present invention have a bromine ion concentration in the color developing solution. Even if the processing is carried out with a high-concentration color developing solution of 5.9 × 10 ^-2 mol / liter, the p of the color developing solution is
It is clear that by adjusting the amount of H and the amount of developing agent, good color developability is exhibited when compared with Comparative Samples 101 to 106.

Example 4 Color developing agent used in Example 3, 2-methyl-4-
[N-ethyl-N- (β-hydroxyethyl) amino]
The aniline sulfate was replaced with 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline sulfate in an equimolar amount, and the color development time was shortened to 2 minutes and 15 seconds.
Photographic properties were examined in the same manner as in Example 3 using the samples 101 to 124 produced in Example 1. As in Example 3, when the sensitivity difference and the color density ratio were determined based on the photographic properties examined after the continuous processing in Example 1, the samples 106 to 124 according to the present invention in this example were the same as those in Example 3. Although almost the same value as the result shown in Table 13 can be obtained, in Comparative Samples 101 to 106, the sensitivity difference is slightly larger than the result shown in Table 13, and the color density ratio is also slightly smaller. ,
It was confirmed that the difference between the inventive sample and the comparative sample is further magnified.

Example 5 Samples 107, 108, 113 and 11 prepared in Example 1
6 samples 122, 124 and 124
No. 3, Jitsuhei 3-39784, a film unit with a lens was produced in accordance with the method described therein. With these six types of film units with lenses, various subjects were photographed under the same conditions, and the color development processing described in Example 3 was performed to obtain color negatives. These color negatives were printed on Fuji Color Paper, Super FA, Type II using Fuji Mini Lab Champin and printer processor FA-140 (manufactured by Fuji Film Co., Ltd. (CP-43FA was used for color development processing at this time)).

It was confirmed that the images obtained by printing were all good, and that the color image storability of color negatives also showed small discoloration and good performance. Also,
The other samples according to the present invention were also carried out, but similarly good results could be obtained.

Example 6 Using the samples 101 to 124 prepared in Example 1, the following color development processing was carried out with an automatic processor, and a photograph was taken according to the method described in (1) of Example 1. I investigated the sex. However, the samples to be examined for photographic properties were processed by separately exposing the samples imagewise for 35 m width and 5 m length each day until the cumulative replenishment amount of the color developing solution was replenished by 3 times the mother liquor tank capacity. The treatment was performed after the cumulative replenishment amount was reached. This process is called process G.

Processing process Processing time Temperature Replenishment amount ^* Tank amount Pre-bath 10 seconds 27 ℃ 13 ml 10 liters Rinse (1) 10 seconds 38 ℃ − − Color development 3 minutes 00 seconds 41 ℃ 30 〃 20 〃 Stop 30 seconds 38 ℃ 20 〃 10 〃 Promote 30 seconds 27 ℃ 6.5 〃 10 〃 Bleach 3 minutes 00 seconds 27 ℃ 6.5 〃 10 〃 Water wash (1) 30 seconds 38 ℃ -10 〃 Water wash (2) 30 Second 38 ℃ 45 〃 10 〃 Fixed arrival 2 minutes 00 seconds 38 ℃ 20 〃 10 〃 Water wash (3) 40 seconds 38 ℃ -10 〃 Water wash (4) 40 seconds 38 ℃ -10 〃 Water wash (5) 40 seconds 38 ℃ 9 〃 10 〃 Rinse (2) 10 seconds 38 ℃ 13 〃 10 〃 * Replenishment amount shows the amount per 35 mm width 1 m length. The rinse (1) is a spray method in which water is sprayed directly onto both sides of the light-sensitive material. 30ml / 35mm width 1
m. Washing with water is a countercurrent method of (2) → (1), (5) → (4) → (3).

The composition of the processing liquid is shown below. (Pre-bath) Mother liquor (g) Replenisher (g) Borax (decahydrate) 20.0 20.0 Sodium sulfate 100 100 Sodium hydroxide 1.0 1.0 Add water 1 liter 1 liter pH 9.25 9.35

(Color development) Mother liquor (g) Replenisher (g) Aminotri (methylenephosphonic acid) -5-sodium salt 1.5 2.0 Sodium sulfite 2.0 2.5 Sodium bromide 1.2 0.8 Sodium carbonate (anhydrous) 25.6 25.0 Sodium bicarbonate 2.7 0.6 N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sesquisulfate monohydrate 4.0 5.5 Add water 1 liter 1 liter pH 10.20 10.27

(Stop) 7.0 ml sulfuric acid 50 ml Water was added to 1 liter (same as mother liquor) pH 0.8 to 1.5

(Promoting) Mother liquor (g) Replenisher (g) Sodium metabisulfite 10.0 12.0 Glacial acetic acid 25 ml 30 ml Sodium acetate 10.0 12.0 Tetrasodium ethylenediaminetetraacetate 1.0 1.2 2- (2-N, N-Dimethylaminoe) Chill) Isothiourea dihydrochloride 3.0 3.6 Add water 1 liter 1 liter pH 2.3 3.8

(Bleaching) Mother liquor (g) Replenisher (g) Gelatin 0.5 0.5 Sodium persulfate 35.0 55.0 Sodium chloride 15.0 20.0 Sodium monophosphate 9.0 12.9 Phosphoric acid (85%) 2.5 ml 2.5 ml 1 liter with water 1 liter pH 2.3 2.4

(Fixing) Mother liquor (g) Replenisher (g) Aminotri (methylenephosphonic acid) -5-sodium salt 1.5 2.1 Ammonium thiosulfate aqueous solution (58 wt%) 185 ml 200 ml Sodium sulfite 10.0 22.0 Sodium bisulfite 8.4 4.0 Water In addition 1 liter 1 liter pH 6.5 7.2

(Rinse (2)) Mother liquor (g) Replenisher (g) Formaldehyde (37%) 1.0 ml 1.5 ml Dry well (manufactured by Fujifilm Corporation) 2.0 ml 2.4 ml 1.0 liter 1.0 liter with water added

Subsequently, the amount of sodium bromide in the mother liquor of the color developing solution was adjusted to 1.50 × 10 ^-2 mol (1.55 g), the replenisher was changed to 1.15 g / liter, and the others were changed without change. Photographic properties were examined in the same manner as in Treatment G of No. 1. This processing is called processing H. The sensitivity difference (ΔS _GH ) between the same samples was obtained for the sensitivities obtained by the treatment G and the treatment H, and the density ratio (D _GH %) was obtained for the color density. The results are shown in Table 14.

[0226]

[Table 14]

The results shown in Table 14 show that Samples 107 to 124 using the cyan couplers represented by the general formula (Ia) and the general formula (II) or the general formula (III) of the present invention are comparative sample 10
It is clear that, as compared with Nos. 1 to 106, even if the bromine ion concentration in the color developing solution is high, the sensitivity and the color density change little, and good color developability is exhibited.

[0228]

The color light-sensitive material containing the cyan coupler represented by the general formula (Ia) and the cyan coupler represented by the general formula (II) or (III) has high sensitivity and high coloring density. And has excellent color image fastness and stable processability. Further, it is possible to provide a silver halide color photographic light-sensitive material excellent in color developability with less deterioration in sensitivity and color density even when color development is performed with a color developer having a high bromine ion concentration. Furthermore, it is possible to provide a color development processing method using a color developing solution having a high concentration of bromine ions.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which contains a cyan coupler represented by the following general formula (Ia). , And the general formula (II) shown in the following chemical formula 2 or the general formula (II) shown in the following chemical formula 3.
A silver halide color photographic light-sensitive material comprising a coupler represented by I). General formula (Ia): In formula (Ia), Za is -NH- or -CH.
(R ₃ )-, Zb and Zc are each -C
Represents (R ₄ ) = or -N =. R ₁ , R ₂ and R
₃ has a Hammett's substituent constant σ p value of 0.20, respectively.
The above-mentioned electron-withdrawing groups are represented. However, σ of R ₁ and R ₂
The sum of p values is 0.65 or more. R ₄ represents a hydrogen atom or a substituent. However, when two R _4's are present in the formula, they may be the same or different. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. In addition, R ₁ , R ₂ , R ₃ , R ₄ or X
The group may become a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. General formula (II) In the formula, R ₁ is —CONR ₄ R ₅ , —SO ₂ NR ₄ R ₅ ,
-NHCOR ₄ , -NHCOOR ₆ , -NHSO
₂ R _6, -NHCONR ₄ R ₅ or -NHSO ₂ NR
₄ R ₅ , R ₂ is a group capable of substituting on the naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, X is a hydrogen atom or an aromatic primary amine developer oxidant. Respective groups that can be separated by a coupling reaction are shown. However, R
₄ and R ₅ may be the same or different and each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₆
Represents an alkyl group, an aryl group or a heterocyclic group. k
When _two or more are present, R _2's may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring.
In addition, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X which is bonded to each other via a divalent or divalent or higher valent group may be formed. General formula (III): In the formula, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group. 2. A silver halide color photographic light-sensitive material according to claim 1, after imagewise exposure, color development, desilvering, washing and / or
Or in the color development processing that performs the stabilization processing step,
A method for processing a silver halide color photographic light-sensitive material, characterized in that color development processing is carried out using a color developing solution having a bromine ion concentration of 1.30 × 10 ^-2 mol / liter or more.